US8530671B2 - Method for preparing a material formed from arborescent-branched molecules comprising associative groups - Google Patents

Method for preparing a material formed from arborescent-branched molecules comprising associative groups Download PDF

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US8530671B2
US8530671B2 US12/810,179 US81017908A US8530671B2 US 8530671 B2 US8530671 B2 US 8530671B2 US 81017908 A US81017908 A US 81017908A US 8530671 B2 US8530671 B2 US 8530671B2
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compound
functions
diglycidyl ether
acid
glycol
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US20100305334A1 (en
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François-Genes Tournilhac
Manuel Hidalgo
Ludwik Leibler
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Centre National de la Recherche Scientifique CNRS
Arkema France SA
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Centre National de la Recherche Scientifique CNRS
Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/785—Polymers containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/85—Polyesters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use

Definitions

  • the present invention relates to a novel method for preparing supramolecular materials.
  • supramolecular materials are materials constituted by compounds linked together by non-covalent bonds, such as hydrogen bonds, ionic and/or hydrophobic bonds.
  • non-covalent bonds such as hydrogen bonds, ionic and/or hydrophobic bonds.
  • One advantage of these materials is that these physical bonds are reversible, in particular under the influence of temperature or by the action of a selective solvent. It is thus possible to envisage using them in fields of application such as coatings (paints, cosmetics etc.), adhesives, hot-melt glues and powder paints.
  • these materials have the advantage of being able to become fluid above a certain temperature, which facilitates their utilization, in particular good mould filling, as well as their recycling. Although they are not constituted by cross-linked polymers but by small molecules, these materials are, like the elastomers, capable of exhibiting dimensional stability over very long periods and of recovering their initial shape after significant deformation. They can be used for manufacturing seals, thermal or acoustic insulation, tyres, cables, cladding, soles of footwear, packaging, patches (cosmetic or dermo-pharmaceutical), wound dressings, flexible hose clips, vacuum tubes, pipes and hoses for conveying fluids.
  • document WO 03/059964 describes a supramolecular material obtained by reacting urea with polyalkylene imines, polyamines or polyamides having in common that they contain free primary or secondary amine functions.
  • the pre-polymer obtained can in particular bear imidazolidone functions and free primary or secondary amine functions which can then react with an alkyl halide.
  • the polyamides can themselves be obtained by condensation of polyamines with dimers and trimers of fatty acids.
  • document WO 2006/016041 discloses a supramolecular material obtained by grafting compounds bearing an imidazolidone group, such as N-aminoethyl-2-imidazolidone (UDETA) onto a polymer such as a PMMA bearing anhydride functions.
  • an imidazolidone group such as N-aminoethyl-2-imidazolidone (UDETA)
  • UDETA N-aminoethyl-2-imidazolidone
  • a supramolecular elastomeric material is moreover disclosed in document WO 2006/087475. It comprises molecules containing at least three associative functional groups, such as imidazolidone groups, which are capable of forming several physical bonds and which can be obtained by reacting urea with the product of the reaction of a polyamine with triacids.
  • the drawback of the preparation methods of the prior art is that they require the use of urea which leads to a release of ammonia.
  • it is necessary to strictly control the operating conditions such as the purity of the reagents, their order of introduction, the duration and the temperature of the reactions, as well as the homogeneity of the mixture.
  • the oligoamidoamine derived from the fatty acid obtained by polycondensation of a polyamine such as diethylene triamine, DETA, or triethylene tetra-amine, TETA, and a fatty acid must meet very specific criteria in terms of purity and degree of polycondensation in order to produce an elastomer.
  • the Applicant has now developed a novel method for the synthesis of supramolecular materials which is easy to implement and does not lead to a release of ammonia, unlike the methods using urea as a reagent.
  • This method also makes it possible to obtain materials containing molecules having a particular branched structure which can endow them with very varied properties depending on the proportions of the reagents used for their synthesis.
  • thermoplastic elastomer i.e. a material capable, at ambient temperature, of being subjected to uniaxial deformation, advantageously of at least 20% for 15 minutes, then of recovering its initial dimension once the stress is removed, with a permanent deformation less than 5% of its initial dimension, and which can be formed or re-formed at high temperature.
  • the novel method according to the invention can moreover make it possible to obtain self-healing materials, i.e. capable, once cut, torn or scratched, of repairing themselves by simply bringing the fractured surfaces back into contact without requiring heating or the application of significant pressure or carrying out any chemical reaction, the material thus repaired retaining elastomeric properties.
  • the method according to the invention consists of reacting, in a first step, a first compound containing a high proportion of molecules which are at least trifunctional with a second at least bifunctional compound, in non-stoichiometric proportions allowing free functions to remain on the first compound, in order to obtain a material that is reacted, in a second step, with a compound bearing one or more associative groups.
  • a subject of the present invention is therefore a method for preparing a material formed from arborescent-branched molecules comprising associative groups comprising the following successive steps:
  • step (b) the reaction of the compound or compounds obtained in step (a) with at least one compound (C) bearing, on the one hand, at least one reactive group capable of reacting with the second functions of (A) and, on the other hand, at least one associative group,
  • R denotes a unit containing at least one primary or secondary amine or alcohol group
  • R′ denotes a hydrogen atom
  • A denotes an oxygen or sulphur atom or an —NH group, preferably an oxygen atom.
  • This method makes it possible to obtain a material comprising arborescent-branched molecules each constituted by fragments that are at least bifunctional and by fragments that are at least trifunctional joined to each other by first bridges, preferably ester or thioester, alone or in combination with second bridges, advantageously amide or urea, said first and second bridges being formed from two functions borne by different fragments, said molecules also comprising, on the fragments situated at the ends of the branches, associative end groups capable of linking together by hydrogen bonds and covalently linked to the functions not involved in said bridges.
  • This material has reversible hydrogen bonds precisely between said associative groups.
  • aromatic-branched is meant according to the invention a branched molecule the backbone of which comprises at least two branchings. This definition does not exclude the possibility of various branchings of the same molecule joining together to form loops.
  • sociative groups groups capable of forming associations with each other by hydrogen bonds, advantageously by 1 to 6 hydrogen bonds.
  • examples of associative groups which can be used according to the invention are the imidazolidinyl, triazolyl, triazinyl, bis-ureyl and ureido-pyrimidyl groups.
  • the average number of associative end groups per molecule of the material is preferably at least 3. It is advantageously at most 6.
  • the latter are linked covalently to the molecule.
  • covalently is meant that the associative groups are connected to the end functions of the molecule either via a direct bond or, preferably, via a chain, in particular alkylene.
  • reactive groups or “functions”, is meant chemical functions capable of reacting with other chemical functions to form covalent bonds, leading in particular to the formation of ester, thioester, amide or urea bridges, and in particular ester and amide bridges.
  • a compound that is “at least bifunctional” denotes a compound bearing at least two, and preferably only two, reactive functions that are identical or different.
  • a compound that is “at least trifunctional” denotes a compound bearing at least three, and preferably only three, reactive functions that are identical or different.
  • fragment is meant within the meaning of the invention a unit of a molecule located between two or three bridges as defined above.
  • a “bifunctional” fragment is capable of being obtained from a bifunctional compound and a “trifunctional” fragment is capable of being obtained from a trifunctional compound.
  • the arborescent-branched molecules according to the invention contain fragments that are at least bifunctional, advantageously bifunctional, and fragments that are at least trifunctional, advantageously trifunctional.
  • Compound (A) utilized in the first step of the method according to the invention can in particular bear at least three functions, identical or different, chosen from the acid, ester or acyl chloride functions. It advantageously comprises from 5 to 100, preferably from 12 to 100 and more preferentially from 24 to 90 carbon atoms.
  • Compound (A) can, in the first step of the method according to the invention, be mixed with mono- and bifunctional compounds, such as mono- and diacids, in particular monomers and dimers of fatty acids.
  • trimers oligomers of 3 identical or different monomers
  • dimers and trimers of fatty acids of vegetable origin These compounds result from the oligomerization of unsaturated fatty acids such as: undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic, docosenoic acid, that are usually found in pine oils (tall oil fatty acids), colza oil, maize oil, sunflower oil, soya oil, grape seed oil, linseed oil, jojoba oil, as well as the eicosapentaenoic and docosahexaenoic acids that are on found in fish oils.
  • unsaturated fatty acids such as: undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic, docos
  • trimers of fatty acids there may be mentioned the compound of the following formula which illustrates a cyclic trimer originating from fatty acids with 18 carbon atoms, knowing that the commercially available compounds are mixtures of steric isomers and positional isomers of these structures, optionally partially or fully hydrogenated.
  • oligomers of fatty acids containing dimers, trimers and monomers of linear or cyclic C 18 fatty acids, said mixture being mainly of dimers and trimers and containing a small percentage (usually less than 5%) of monomers.
  • said mixture comprises:
  • dimer/trimer mixtures of fatty acids % by weight:
  • the products Pripol®, Unidyme®, Empol®, and Radiacid® contain monomers of C 18 fatty acids and oligomers of fatty acids corresponding to multiples of C 18 .
  • compound (A) instead of triacids, it is possible to use, as compound (A), a compound containing at least three ester or acyl chloride functions.
  • ester there may be mentioned a methyl, ethyl or isopropyl ester (preferably methyl) of a trimer of fatty acid or of a mixture of oligomers of fatty acids as defined above.
  • compound (A) can be a compound that is at least trifunctional containing at least two different functions, advantageously chosen from the acid, ester and acyl chloride functions.
  • compound (B) contains at least two functions, identical or different, capable of reacting with compound (A), chosen in particular from the epoxy, alcohol and amine functions. It can also include other functions that are not capable of reacting with compound (A).
  • Compound (B) is preferably a diepoxide. It can therefore be chosen from: bisphenol A diglycidyl ethers, bisphenol F diglycidyl ether, tetrabromo bisphenol A diglycidyl ether, or hydroquinone diglycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentylglycol dig
  • compound (B) can be a polyepoxide containing at least three epoxide functions, chosen for example from: castor oil triglycidyl ether, 1,1,1-tris(hydroxymethyl) propane triglycidyl ether, trisphenol triglycidyl ether, glycerol triglycidyl ether, glycerol propoxylate triglycidyl ether, glycerol ethoxylate triglycidyl ether, trimethylol propane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritolpolyglycidyl ether, poly(glycidyl acrylate), polyglycidyl methacrylate, epoxidized polyunsaturated fatty acids, epoxidized vegetable oils, epoxidized fish oils and epoxidized
  • compound (B) can be a diol.
  • compound (B) can be chosen from: ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, octanediol, nonanediol, decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyesters with hydroxy ends, polybutadienes with hydroxy ends, polydimethylsiloxanes with hydroxy ends, polyisobutylenes with hydroxy ends, polybutadiene-co-acrylonitrile copolymers with hydroxy ends, diol dimers originating from fatty acids and mixtures thereof.
  • compound (B) can be a polyol containing at least three alcohol functions.
  • examples of such compounds are in particular: sugars such as sorbitol, pentaerythritol, trimethylolpropane, as well as glycerol and its ethoxylated and propoxylated derivatives, castor oil and diol diners originating from fatty acids such as Pripol 2033 from Uniqema.
  • the ratio of the number of the reactive functions of compound (B) to the sum of the functions of compound (A) ranges from 0.1 to 0.8 and preferably from 0.3 to 0.8.
  • the compound obtained on completion of the first step of the method according to the invention is reacted, in the second step, with a compound (C) bearing at least one reactive group and at least one associative group, so that the reactive groups of (C) react with the second functions, i.e. the remaining reactive functions of compound (A).
  • Compound (C) bears at least one reactive group which can in particular be chosen from the primary or secondary amine or alcohol groups. In a variant, compound (C) can bear at least two such identical or different groups. It also bears an associative group chosen from the nitrogenous, preferably diazotized heterocycles. Compound (C) corresponds more precisely to any one of formulae (C1) to (C3):
  • R denotes a unit containing at least one primary or secondary amine or alcohol group
  • R′ denotes a hydrogen atom
  • A denotes an oxygen or sulphur atom or an —NH group, preferably an oxygen atom.
  • Preferred examples of compounds (C) are 2-aminoethylimidazolidone (UDETA), 1-(2-[(2-aminoethyl)amino]ethyl)imidazolidone (UTETA), 1-(2- ⁇ 2-[(2-aminoethylamino]ethyl ⁇ amino)ethyl]imidazolidone (UTEPA), 3-amino-1,2,4-triazole (3-ATA) and 4-amino-1,2,4-triazole (4-ATA).
  • the material according to the invention comprises binding bridges, preferably ester, formed in the first step of its synthesis method, by reaction of the functions (advantageously epoxide) of compound (B) with reactive functions, so-called “first functions” (advantageously acid functions), of compound (A) and of the binding bridges (advantageously amide), formed in the second step of this method, by reaction of the remaining reactive functions (preferably acid), so-called “second functions”, of compound (A) with reactive groups (advantageously amine) of compound (C).
  • This material also contains hydrogen bonds between the associative groups borne by the molecules which constitute it.
  • the arborescent-branched molecules constituting said material contain a soluble fraction, as well as optionally an insoluble fraction, i.e. a fraction representing from 0.1 to 90% of the weight of the material and which is not soluble in any proportion in any solvent.
  • the number average molecular mass of the soluble fraction is preferably comprised between 300 and 300,000 g/mol, as measured by GC.
  • the average number of associative end groups per molecule is at least 1.2, preferably of at least 2, or even at least 2.2.
  • this material can contain molecules other than the arborescent-branched molecules described previously, in particular in the case where compound (A) contains trimers of fatty acids mixed with mono- and/or dimers of fatty acids.
  • the material according to the invention contains at least 25% and, better, at least 50% by number said arborescent-branched molecules.
  • this material also contains intermolecular hydrophobic bonds, advantageously due to interactions between alkyl groups borne by each of the arborescent-branched molecules described previously.
  • alkyl is meant within the meaning of the invention side groups (C n H 2n+1 ) and not alkylene chains (C n H 2n ), for example.
  • each of these molecules comprises C 6 -C 24 alkyl chains, advantageously in greater numbers than said associative end groups. They can in particular be provided by the compounds (A), in particular when they are trimers of fatty acids.
  • the proportions of (A), (B) and (C) used in the method according to the invention determine the mechanical characteristics of the material obtained.
  • This, material advantageously has elastomeric properties, i.e. the property of being able to be subjected to uniaxial deformation at ambient temperature and to recover its initial dimension once this stress is removed, with a permanent deformation of less than 5% of its initial dimension.
  • seals thermal or acoustic insulation, tyres, cables, cladding, soles of footwear, packaging, coatings (paints, films, cosmetics), patches (cosmetic or dermo-pharmaceutical) or other systems for trapping and releasing active ingredients, wound dressings, flexible hose clips, vacuum tubes, pipes and hoses for conveying fluids, and generally components requiring good resistance to tearing and/or fatigue, rheological additives or additives for hot-melt glues and adhesives.
  • the material according to the invention can be used as it is or in single-phase or multi-phase mixtures, with one or more compounds such as petroleum cuts, solvents, mineral and organic fillers, plasticizers, tackifying resins, anti-oxidants, pigments and/or colorants, for example, in emulsions, suspensions or solutions.
  • one or more compounds such as petroleum cuts, solvents, mineral and organic fillers, plasticizers, tackifying resins, anti-oxidants, pigments and/or colorants, for example, in emulsions, suspensions or solutions.
  • this material can be used for the manufacture of a cosmetic composition usually containing a physiologically acceptable medium, i.e. compatible with keratinous substances.
  • the Soxhlet cartridge was filled with 20 g of anhydrous magnesium sulphate.
  • the oil bath was then heated to reflux of the toluene, the reaction is monitored by observing the reduction in the infrared signal of the acid at 1710 cm-1 and the increase in that of the ester at 1740 cm-1. After reacting for 2 hours at 140° C. (temperature of the oil bath), it is noted that these bands no longer exhibit any particular change. 3.08 g of UDETA (24 mmol) is then added and the mixture is left to react again for 3 hours at 140° C. (temperature of the oil bath)
  • the solvent is then evaporated off under vacuum at 50° C. using a rotary evaporator then the content of the flask is placed under primary vacuum until degassing is completed (24 hours).
  • the product obtained is a viscoelastic liquid, which is capable, when applied hot (100° C.) to both glass and to a metal surface (aluminium or steel), of spreading easily in order to form an adhesive film.

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US12/810,179 2007-12-24 2008-12-19 Method for preparing a material formed from arborescent-branched molecules comprising associative groups Expired - Fee Related US8530671B2 (en)

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FR0760341 2007-12-24
FR0760341A FR2925505B1 (fr) 2007-12-24 2007-12-24 Procede de preparation d'un materiau forme de molecules arborescentes comportant des groupes associatifs
PCT/FR2008/052379 WO2009081065A2 (fr) 2007-12-24 2008-12-19 Procède de préparation d'un matériau forme de molécules arborescentes comportant des groupes associatifs

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Cited By (2)

* Cited by examiner, † Cited by third party
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US20110003872A1 (en) * 2007-12-06 2011-01-06 Arkema France Material formed from dendritic molecules containing associative groups
US20120022221A1 (en) * 2009-04-02 2012-01-26 Arkema France Use, as a Shock Absorber, of a Material Formed from Branched Molecules Containing Associative Groups

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* Cited by examiner, † Cited by third party
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FR2946350B1 (fr) * 2009-06-04 2012-05-11 Arkema France Utilisation de molecules porteuses de groupes associatifs comme durcisseurs de resines thermodurcissables
FR2950351B1 (fr) * 2009-09-23 2011-11-18 Arkema France Composition comprenant un melange d'elastomere et de polymere supramoleculaire
FR2965408A1 (fr) * 2010-09-23 2012-03-30 Arkema France Materiau composite et utilisation pour la fabrication d'une electrode
FR2975101B1 (fr) * 2011-05-10 2013-04-26 Arkema France Resines et composites hybrides thermodurs / supramoleculaires pouvant etre faconnes a chaud et recycles
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US20100305334A1 (en) 2010-12-02
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